Pentahalophenylethylsilanes and siloxanes



United States Patent ABSTRACT OF THE DISCLOSURE Monomers, homopolymers and copolymers or organosilicon compounds of the formula [(CuFlX) CH OHflnS'iO Rm 2 are disclosed. Illustrative of this class of compounds is The novel compounds have utility as coating compounds, holding compounds, lubricants, and as ingredients in silicone elastomer stocks.

This application relates to new organopolysiloxane fluids, resins, and elastomers which exhibit superior thermal stability, and which have utility as coating compounds, molding compounds, lubricants, and as ingredients in silicone elastomer stocks.

vThe organosilicon compounds of this invention comprise at least one unit, where X is chlorine, bromine or fluorine, R is any monovalent hydrocarbon, monovalent halohydrocarbon other than C F XCH CH divalent hydrocarbon or halohydrocarbon radical having both valences bonded to silicon atoms, monovalent cyanoalkyl, monovalent mercaptoalkyl, monovalent aminoalkyl, monovalent alkylene ester, monovalent alkylether, hydrolyzable, hydrogen, or hydroxyl radical, n is an integer of 1 to 4, and m is an integer of 0 to 3.

R can be any monovalent hydrocarbon radical, e.g., alkyl and cycloalkyl radicals such as methyl, isopropyl, sec-hexyl, octyl, octadecyl, and cyclohexyl; aliphatically unsaturated radicals such as vinyl, ethynyl, allyl, cyclopentenyl, and 3-octeuyl; and aryl-containing radicals such as phenyl, tolyl, benzyl, xenyl, or naphthyl.

R can also be any monovalent halohydrocarbon radical such as 3,3,3-trifluoropropyl, 4,5-dichlorooctyl, bromocyclohexenyl, 3-ch1oroallyl, dibrornophenyl, a,u,a-trifluorotolyl, and fluoroxenyl; any monovalent cyanoalkyl radical such as cyanomethyl, gamma-cyanopropyl, 3-cyanocyclohexyl, fi-cyanooctyl, and gamma-cyanoisobutyl; any monovalent mercaptoalkyl radical such as mercaptomethy-l, 18- mercaptoethyl, gamma-mercaptopropyl, gamma-merca-ptoisobutyl, 3-mercaptocyclohexyl, and delta-mercaptodecyl; any monovalent aminoalkyl radical such as gamma-aminopropyl, gamma-aminoisobutyl, Z-amino-cyclopentyl, aminohexyl, CH CH CH NHCH CH NH Patented Jan. 21, 1969 and C(CH CH CH NH any monovalent alkylene ester radical such as 0 II C (CHzCHzGHzO 0 CH3, CH2ZHO 00 0 ll CHzCH COCHCH C(CHs)s and C4Hsl )O(CHzCHzO)4CaH1 and any monovalent alkylether radical such as and CH CH OCH CH OCH By alkylene ester radical is meant any radical of the formula -ZAZ, where Z is an alkylene radical, A is a carboxyl linkage, and Z is a monovalent hydrocarbon radical or a monovalent alkylether radical.

By alkylether radical is meant any alkyl-endblocked radical containing at least one ether linkage and at least one alkylene radical.

By aminoalkyl radical is meant any monovalent radical consisting of at least one alkylene radical and at least one amino group.

R can further be any divalent hydrocarbon or halohydrocarbon radical, e.g., methylene, dimethylene,

phenylene,

c memo F20 H20 11?, -Q

013 and CH2CHC H2- Both valences are bonded to silicon atoms, for example ESiCH CH SiE.

R can also be any hydrolyzable group, i.e., and siliconbonded radical that reacts with water to form a silanol group. Examples are halogens such as chlorine and bromine; alkoxy groups such as methoxy, ethoxy, beta-chloroethoxy, isopropoxy, and hexoxy; alkoxyalkoxy groups such as beta-ethoxyethoxy, beta-methoxyethoxy, and betamethoxypropoxy; acyloxy groups such as formate, acetate, trifluoroacetate and butyrate; ketoxime derivatives such as amino groups such as NH methylamino, dimethylamino and oxyamino radicals such as -ON(CH etc., and the isocyanate radical.

More specifically, this application relates to an organosilicon compound consisting essentially of at least one unit of the formula n 4X) 2 2]n O4 m m 2 any other units present being of the formula Rusiq where X is selected from the group consisting of chlorine, fluorine and bromine, R is selected from the group consisting of monovalent hydrocarbon, monovalent halohydrocarbon other than C F XCH CH divalent hydrocarbon or halohydrocarbon radicals having both valences bonded to silicon atoms, monovalent cyanoalkyl, monovalent mercaptoalkyl, monovalent aminoalkyl, monovalent alkylene ester, monovalent alkyl ether, hydrolyzable, hydrogen, and hydroxyl radicals, m is an integer of to 3, n is an integer of 1 to 4, R is selected from the group consisting of monovalent hydrocarbon, monovalent halohydrocarbon, monovalent cyanoalkyl, monovalent mercaptoalkyl, monovalent alkylene ester, monovalent alkyl ether, hydroxyl, hydrogen, and monovalent aminoalkyl radicals, and x is an integer of O to 3.

Examples of the classes of R are listed above.

The compositions of this invention can be silanes, such as CF5CH2CH2Si(OcH )3,

They can also be homopolymers such as (CaF5CH2CH2?lO)z5 The compounds of this invention can be made in a number of ways. One method is to react C F CH=CH C F BrCH CH or C F ClCH=CH with an ESlH compound at elevated temperatures in the presence of chloroplatinic acid.

Another method is to react pentafluorobenzene, tetrafiuorobromobenzene, or tetrafluorochlorobenzene with an ESiCH:CH compound at elevated temperatures in the presence of AlCl Pentafluorobenzene and pentafluorostyrene are commercially available. Tetrafiuorochlorobenzene is known to the art, and a method for making tetrafluorobrornobenzene is disclosed in the copending US. patent application No. 396,391, filed Sept. 14, 1964.

Also, the polysiloxanes of this invention can be prepared by hydrolysis of the appropriate silanes of this invention by any of the well-known techniques for hydrolysis.

The following examples are illustrative only and should not be construed as limiting the invention, which is properly delineated in the appended claims.

Example 1 (a) 38.8 g. of pentafluorostyrene and 0.004 g. of chloroplatinic acid which was dissolved in 0.04 cc. of isopropanol were mixed and heated to 80 C. T this, 23.6 g. of dimethylchlorosilane were added dropwise, and the mixture was heated at 55 to 60 C. for 2 hours.

An additional 0.04 cc. of the chloroplatinic acid solution was then added, and the mixture was further heated at 55 to 60 C. for another 8 hours.

Fractionation yielded liquid C F CH CH Si(CH Cl (B.P. l03-104 at 11 mm.; 11 1.4440) in 47.8% yield.

(b) 28.9 g. of this product were dissolved in 50 ml. of diethylether and added with stirring to an equal weight mixture of water and diethylether.

The ether phase was then washed with water until neutral, and then it was freed of water and ether.

The product was mixed with 0.25 g. of sodium hydroxide, and distilled at reduced pressure.

[C F CH CH Si(CH O was recovered in nearly a quantitative yield (B.P. 150-151 C. at 4.0 mm.; 11 1.4430).

Example 2 38.8 g. of pentafluorostyrene and 0.004 g. of chloroplatinic acid which was dissolved in 0.04 cc. of isopropanol were mixed and heated to C.. 33.9 g. of trichlorosilane were added dropwise to the solution. An exothermic reaction took place. The reaction temperature was maintained at to C. by controlling the trichlorosilane addition rate.

At the end of the reaction, fractionation yielded an 84% yield of liquid C F CH CH SiCl (B.P. 109110 C. at 15 mm.; 11 1.4575).

19.6 g. of C F CH CH SiCl were dissolved in 75 ml. of diethylether and added with stirring to 26 g. of water. The ether phase was washed until neutral with water.

A film of the resulting silane hydrolyzate was cast onto an infrared spectroscopic prism by applying the ether phase to the prism and allowing the ether to evaporate.

The treated prism was heated for 100 hours at 200 C. and then heated for 150 hours at 250 C. with periodic infrared measurements being taken.

It was determined that the film first lost ESlOH bonds and gained ESlOSiE bonds as condensation went to completion. Following that, the disintegration of the film proceeded with an uniform decrease in the number of all bonds present, indicating slow evaporation of the film, but there was no marked deterioration in the film that remained, and no marked cleavage of any particular bond.

The extrapolated life of a M inch film of the condensate was estimated to be about 10.000 hours at 250 C.

Example 3 55.4 g. of chlorotetrafluorobenzene were vigorously stirred with a few grams of AlCl 24.2 g. of vinyltrichlorosilane were then added in a dropwise manner with stirring, and the mixture Was heated with stirring for 4 /2 hours.

Distillation yielded 8 g. of a product with a boiling point of 142 to 145 C. at 18 mm. of pressure. The major component of the distillate was C F ClCH CH SiCl Example 4 (a) The experiment of Example 1(a) was repeated, substituting methyldichlorosilane for dimethylchlorosilane. The product was d scHzcHzsi C12.

(b) 15 molar parts of the above were cohydrolyzed with 10 molar parts of trimethylchlorosilane and 75 molar parts of dimethyldichlorosilane to form a fluid having a viscosity of 46.3 cs. at 25 C.

(c) 15 molar parts of the product of (a) above were cohydrolyzed with 10 molar parts of trimethylchlorosilane, and 5 molar parts of dichlorophenyltrichlorosilane to form a fluid having a viscosity of 74.8 cs. at 25 C.

(d) 2 mls. each of fluids (b) and (c) above were placed in separate 20 ml. beakers, 2 mls. of a trimethylsiloxy-endblocked dimethylpolysiloxane having a viscosity of 116 cs. at 25 C. were placed in a third 20 ml. beaker.

The beakers were heated at 250 C., and the time required until the fluids gelled was recorded.

Fluid: Gel time, hrs. Dimethylpolysiloxane 16 to 24 (b) 48 to 56 (c).. 64 to 72 (e) Both (a) and (b) showed superiority over both dimethylpolysiloxane and a commercial dichlorophenylphenyl-methylpolysiloxane lubricant as high speed ball bearing lubricants, in that less scarring of the ball bearings occurred when (a) or (b) were used.

Example 5 When 5 g. of tetrafluorochlorostyrene and 0.1 g. of a chloroplatinic acid complex with cyclohexene are reacted at 80 C. with 3 g. of

HSlCHflOHICHiCN,

[ONC(CH3):]I and the product is neutralized,

CnFtOlCHzCHflSlCHgCHzCHzCN NC( Ha)$l2 is recovered.

Example 6 When 1 g. of tetrafluorobromostyrene, 2 g. of octadecene-l, and 0.01 g. of chloroplatinic acid complex with ethylene, are reacted with 0.5 g. of

r HO SIiO H at 50 C., a silanol-endblocked product containing Example 7 When 1 g. of pentafl-uorostyrene is reacted with 0.8 g. of

units is formed.

in'the presence of a trace of chloroplatinic acid, the compound is formed.

Example 8 When 1 g. of tetrafluorochlorostyrene is reacted with 1 g. of

CH3 0 HSiCHzCHzCHz OCH;

z by heating the mixture in the presence of platinized carbon, the product CH3 0 CalHClCHzCHzEiiCHzCHgCHz OCH;

H: is formed.

Example 9 When 1 g. of pentafiuorostyrene is reacted with 5 g. of

0H, 0H; msio S i(C3HgO)5CHa (5H2 JlHg m Ha in the presence of chloroplatinic acid by heating at C., the product Example 10 When 1 g. of SiCl 1 g. of magnesium powder, and 5 g. of C F CH CH Cl are heated at C., the product Si(CH CH C F is formed.

That which is claimed is:

1. An organosilicon compound of the unit formula where X is chlorine, bromine or fluorine, R is any monovalent hydrocarbon, monovalent halohydrocarbon other than C F XCH CH divalent hydrocarbon or halohydrocarbon radical having both valences bonded to silicon atoms, monovalent cyanoalkyl, monovalent mercaptoalkyl, monovalent aminoalkyl, monovalent alkylene ester, monovalent :alkylether, hydrolyzable hydrogen, or hydroxyl radical, n is an integer of 1 to 4, and m is an integer of 0 to 3.

2. An organosilicon compound consisting essentially of at least one unit of the formula [(C0F4X)CH2CH2L1S':lO

M m 2 the remaining units present being of the formula R xs10 where X is selected from the group consisting of chlorine, fluorine and bromine, R is selected from the group consisting of monovalent hydrocarbon, monovalent halohydrocarbon other than C F XCH CH divalent hydrocarbon or halohydrocarbon radicals having both valences bonded to silicon atoms, monovalent cyanoalkyl, monovalent mercaptoalkyl, monovalent aminoalkyl, monovalent alkylene ester, monovalent alkyl ether, hydrolyzable, hydrogen, and hydroxyl radicals, m is an integer of 0 to 3, n is an integer of 1 to 4, R' is selected from the group consisting of monovalent hydrocarbon, monovalent halohydrocarbon, monovalent cyanoalkyl, monovalent mercaptoalkyl, monovalent alkylene ester, monovalent alkyl 7 8 ether, hydroxyl, hydrogen, and monovalent aminoalkyl 10. A homopolymer of radicals, and x is an integer of to 3.

CH3 3. The compound of claim 2 where X is fluorine. l. 4. C F CH CH SiCl rm CFCHQCHMO 5. C F CH CH Si(CH Cl. 5 u l 6. C F C1CH CH SiCl f rences Cited 7, UNITED STATES PATENTS (I311, 2,911,427 11/1959 Brown 260-4482 2 911428 11/1959 Tarrant 260--448.2 H 1 D I meme 10 3,109,855 11/1963 Pummer et a1. 260448.2 p y of 3,122,521 2/1964 Pierce 260448.2 X CH1 3,269,928 8/1966 Haszeldine et a1. 260448.2 X 06mm) 3,270,070 8/1966 Haszeldine et a1. 260448.2 x

(CH SiO, and (CH SiO units. 15 HELEN M. MCCARTHY, Primary Examiner.

9. Apolymer 0f PAUL F. SHAVER, Assistant Examiner.

CH2 C5F CH1CH1S1C1; US. Cl. X.R.

(CH SiO, 0 11 0 510 and (CH SiO units. 260-4483 46-5;

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 ,423,445 January 21 1969 George W. Holbrook et al.

It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below: Column 2, lines 3 and 4, the first formula should appear as shown below:

-CH CH CH OCCH same column 2, lines 9 and 10, the first formula should appear as shown below:

Column 3, lines 39 to 42, the formula should appear as shown below:

C P CH CH2S1O1/2 (C F5CH2CH2SiO)2 CH CH CH NH 2 CH same column 3 lines 44 to 47 the formula should appear as shown below:

Column 7, lines 12 to 14, the formula should appear as shown below:

Signed and sealed this 28th day of April 1970.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. WILLIAM E. SCHUYLER, JR.

Attesting Officer Commissioner of Patents 

